Accelerators



These materials, which are described atnt Qfilic Patented Sept. 2, 1958AccELEnAroRs Nelson V. Seeger, Silver Lake, Cuyahoga Falls, and ThomasG. Mastin, Akron, Ohio, assignors, by mesne assignments, to The GoodyearTire & Rubber Company, a corporation of Ohio No Drawing. ApplicationSeptember 26, 1955 Serial No. 536,760

5 Claims. (Cl. 260-454) This invention relates to accelerators for cureof synthetic elastomeric polymers. More particularly it relates tomethods for and the cured elastomeric polymers resulting from theacceleration of the reaction between polyisocyanates and uncuredelastomeric diisocyanatemodified polyesters and polyesteramides such asthose described in United States Patents 2,625,532 and 2,625,- 535 andin our copending applications Serial Numbers 305,914, filed August 22,1952, Patent No. 2,777,831; 307,900, filed September 4, 1952, Patent No.2,760,953. in detail below, will hereinafter be referred to as uncuredelastomeric diisocy- .anate-modified polyesters.

It has been known to use water and water-liberating compounds, such assalts carrying water of crystallization,

in the preparation of cured diisocyanate-modified polyesters. Suchmaterials are known to accelerate the cure of elastomericdiisocyanate-modified polyesters. However, the use of such materials isnot entirely satisfactory because the reactions involved produce CO gaswhich causes blisters or bubbles in the cured product. In addition thewater reacts with the isocyanate radicals present with the result thatmore polyisocyanate than that normally required must be added to effecta complete cure.

It is therefore an object of this invention to provide accelerators forthe cure of uncured elastomeric diisocyamate-modified polyesters whichdo not produce the objectionable results obtained by using water orwater-lib crating compounds. Other objects will appear as thedescription proceeds.

According to the practice of this invention, the uncured elastomericdiisocyanate-modified polyester, such as those described in the patentsand our copending applications referred to above, is mixed with thepolyisocyanate required to effect a cure of the elastomer and, inaddition, with the accelerator referred to above, this being acondensation product of a primary amine and an aldehyde. Thecondensation product accelerates the reaction between the -NCO groups ofthe polyisocyanate and the urethane, urea, or amide linkages presentalong the molecular chains in the modified polyester and thus effects anaccelerated cure with consequent saving of time and increased productionfrom each unit of equipment.

The aldehyde/ amine condensation products which have been found usefulin the practice of this invention are those resulting from thecondensation reaction between approximately one molecular proportion ofa primary organic amine with from two to five molecular proportions ofan aliphatic aldehyde having a plurality of carbon atoms. Thesecondensation products, usually prepared in the presence of an organicacid catalyst, are generally liquids. Examples of the amines which maybe used in the preparation of these condensation products are aniline,butylamine, methylamine, o-toluidine, and diethylamine. Among thealdehydes which are useful in preparing these condesnation products maybe mentioned propionaldehyde, butyraldehyde, heptaldehyde, andbenzaldehyde. Particularly efiective condensation products which may beused in the practice of this invention are those resulting from thereaction of approximately 4 mols of butyraldehyde with 1 mol of anilineor with 1 mol of butylamine. Further description of these condensationproducts and methods for their preparation will be found in UnitedStates Patents 1,780,326 and 1,780,334.

The amount of amine/aldehyde condensation product required to acceleratethe reaction between the polyisocyanates and the diisocyanate-modifiedpolyester will, of course, vary depending upon the condensation productused and upon the other ingredients used in compounding the elastomer.In general, there may be used as little as 0.05 part or as much as 10parts of the accelerator by weight per parts of elastomeric polymer byweight. A preferred range is from 0.10 to 2.5 parts by weight per 100parts of polymer. In general it may be said that the degree ofacceleration is proportional to the amount of accelerator used, since,normally, increased amounts of accelerator will reduce the time requiredto effect a cure. Excessive amounts of these condensation products willproduce the acceleration desired, but are sometimes to be avoided eitherbecause the time required to effect the cure is so short as tocomplicate the production operations involved in fabricating a finishedarticle, or because the polymer cured with excess accelerator hasundesirable or interior physical properties.

While each class of the uncured elastomeric diisocyanate-modifiedpolyesters has been fully described in the patents and applicationsreferred to above, the general chemical reactions involved in theirpreparation may be represented by the following illustrations in whichR, R, and R" denote divalent organic radicals.

in which n is a positive whole number denoting the degree ofpolymerization of the polyester formed.

PREPARATION OF POLYESTERAMIDE n(H0RNHz) HO-ii-lV-ii-OH) t t tH(O-R-NCRO),.0H zn-nmo PREPARATION OF UNCURED DIISOCYANATE- MODIFIEDPOLYESTER HO-polyester-OOOH OCNR"NCO 0 H H O H g, I H II(HO-polyester-Ol R"- CO-p0lyester-C)mOHmC Oz in which m is a positivewhole number denoting the number of segments in thediisocyanate-modified, chain-extended polymer.

PREPARATION OF UNCURED DIISOCYANATE- MODIFIED POLYESTERAMIDEHO-polyesteramide-C O OH 0 CNRNC O H O H I II I(HO-polyesteramide-O-b'l-RNO-O-polyes teramlde-M-OH-l-mOO;

in which in is a positive whole number denoting the number of segmentsin the diisocyanate-modified, chain-extended polymer.

PREPARATION OF UNCURED DIISOCYANATE- MODIFIED INTERPOLYMERS' groups inthe curing'agent' and the reactive hydrogensi in certain groups presentin the chain of'the extended polymer and certain terminal groups at theends of the chainextended units. The'terminal groups include, of course,hydroxyl, carboxyl, and amino radicals. The groups along the chaininclude the ,groups formed by reaction between an NCO group and acarboxyl, hydroxyl, or amino group, and may be'represented. as asubstitute amide linkage respectively. Each of these groupings has atleast one active hydrogen available for reaction With the --NCO group ofthe polyisocyanate'used to etle'cta cure.

The uncured elastomeric v diisocyanate-modified polyesters andpolyesteraniides described at length in our patentsandcopending'applications referred to above may be grouped in four generalclasses- First, the reaction product of (1) a polyester or"polyesteramide prepared from at least one dibasic carboxylic acid. and'atleast one glycohand/orat leastone amino alcohol, and/or atleast onediamineythe number of hydrogen-bearing amino groups being present in anamount 4, 4,4'-tolidine diisocyanate; 1,5-naphthalene diisocyanate;4,4'-diphenyl ether diisocyanate, and p-phenylene diisocyanate, thediisocyanate being used in an amount ranging from 0.70 to 0.99 (apreferred range is from 0.90 to 0.99) mols per mol of polyester orpolyesteramide.

Second, the reaction product 'of (1) a polyester or polyesteramideprepared from at least one dibasic carboxylic acid, and at least oneglycol, and/or at least one amino alcohol and/or at least 'one-diamine,the number not to exceed 7.5% of the total hydroxyland hydrogen-, 7

bearing amino groups present, the polyester or polyester- .amide havinga hydroxyl number from 40 to 100 (a preferred range is fromtoand'aiiacid'number from 0 to 7; and (2) at least one diisocyanateselected from the group consisti'nglof 4,4f -diph'enyl diisocyanate;4,4'-d iphenylene metha'ne'diisocyahate, dianisidine diis'ocyanate;

of. hydrogen-bearing amino groups present being in: an amount not toexceed 30% 'oft-he total hydroxyl and-hydrogen-bearing amino groupspresent, the polyester or polyesteramide having a hydroxyl number-from30 to 140 (a preferred range is from 50 to 60) "and an acid number from0 to 12; and (2) at least one tolylene diisocyanate, the diisocyanatebeing usedin' an amount ranging from 0.85 to 1.10 (a preferred range isfrom 0.90 to 1.00) mols permol of polyester orpolyesteramide.

Third, the reaction product resulting from the reaction of a'mixturecomprising (1) a polyester prepared from bifunction'al ingredientsincluding at least one dibasic carboxylic acid containing at leastthreecarbon atoms, and at least'one glycol, said polyester having ahydroxylnumb'er from 30 to 140 (a preferred range is'from 50 to 60) andan acid number from 0 to 12; (2) at least one bifunctional additiveselected from the group consisting of diarnines, amino alcohols,dicarboxylic acids, hydroxy carbdXylic aeids,: amino carboxylicacids-and the ureas,-. guanidines, andthioureas containing a pr-imaryamino group, said bifunctional additive being used in an amount suchthat the total number of NH and -.-COOH equivalents present in saidbifunctional reactant shall be from 0.06 to 0.24 equivalent per mol of-polyester, and (3) at least one tolylene diisocyanate, thediisocyanatebeing used in an amount. equal to the sum of from 0.85 molsto 1.10 (apreferred range is from 0.90 to 1.00) mols of diisocyanate per'rn'ol ofp'olyester plus 'thC: molar amount of diisocyanate equivalent to themols of said bifunctional additive used.

Fourth, the-reaction product resulting from the reaction of. a1 miirturecomprising (1.) a polyester prepared from bifurictional ingredientsincluding at least one 1 dibasic carboxylic" acid" containing at leastthree carbon atoms and atl'east one glycol, said polyester having ahydroxylnumher between 40 and 100 (a preferred range is from- 50 to 60)and an acid number from 0- to 7;v (2) at least-one bifunctional additivefrom the group consisting of -diamines, amino alcohols, dicarboxylicacids, hydroxy carbox fic' acids, aminocarboxylic acids and the ureas,guanidines, and thioureas containing a primary aminogroup, saidbifunctional additive being used in an amount such that total number of--NH 'and C0 0H-equivalents present in such bifunctional reactantshallbe from. 0.06' to 0.48 equivalent per mol of polyester, and (3) atleast one diisocyanate selected from the: group consisting of 4,4diphenyl diisocyanate; 4,4-diphenylenemethane 'diisocyanate;4,4'-tolidine diisocyanate, dianisidine diisocyanate; 1,5-naphthalenediisocyanate; 4,4-diphenyl ether diisocyanate, and p-phenylenediisocyanate, the diisocyanate being used in an amount equal to thesumof from 0.70 mol to'0.99- (apreferred range is from 0.90 to 0.99) mol ofdiisocyanate per mol of, polyester plus the molar amount of diisocyanateequivalent to the mols of bifunctional additive used.

Listedrbelow'are the reactants used toform some'preferred polyesters andpolyesteramides' which, when prepared and subsequently: modifiedby adiisocyanate'or other. additive in. accordance with the appropriate:limitationsindicated in the description of the four types of .synthetic'elastomers; 'Wlll produce elastomeric products;

(1) Ethylene glycol-plus adipic acid.

(2) Propylene glycol 1,2 plus adipic acid. ('3) Ethylene glycol molpercent), propylene-glycol 1,2 (2011 101. percent) plus adipic acid. a

aeeoare (4) Ethylene glycol (80 mol percent), propylene glycol 1,2 (20mol percent) plus azelaic acid.

(5) Ethylene glycol (80 mo? percent), propylene glycol 1,2 (20 molpercent) plus sebacic acid.

(6) Ethylene glycol 80 mol percent), propylene glycol 1,2 (20 molpercent) plus dilinoleic acid (20 mol percent), adipic acid 80 molpercent).

(7) Ethylene glycol (80 mol percent), glycerine monoethyl ether (20 molpercent) plus adipic acid.

(8) Ethylene glycol (80 mol percent), butylene glycol 1,4 (20 molpercent) plus adipic acid.

(9) Ethylene glycol (80 mol percent), propylene glycol 1,3 (20 molpercent) plus adipic acid.

(10) Ethylene glycol (80 mol percent), pentane diol 1,5 (20 mol percent)plus adipic acid.

(11) Ethylene glycol (80 mol percent), glycerine monoisopropyl ether (20mol percent) plus adipic acid. (12) Ethylene glycol (80 mol percent),propylene glycol 1,2 (from 18 to 5 mol percent), ethanol amine (from 2to mol percent), plus adipic acid.

(13) Ethylene glycol (80 mol percent), propylene glycol 1,2 mol percent)plus maleic acid (from 3 to 6 mol percent), adipic acid (from 97 to 94mol percent).

(14) Ethylene glycol (80 mol percent), propylene glycol 1,2 (from 19 to17 mol percent), piperazine (from 1 to 3 mol percent) plus adipic acid.

(15) Ethylene glycol (80 mol percent), propylene glycol 1,2 (from 18 to5 mol percent), dihydroxyethyl aniline (from 2 to 15 mol percent) plusadipic acid.

(16) Ethylene glycol (80 mol percent), diethylene glycol (20 molpercent) plus adipic acid.

(17) Ethylene glycol (from 90 to 10 mol percent), propylene glycol 1,2(from 10 to 90 mol percent) plus adipic acid.

(l8) Ethylene glycol (from 90 to 10 mol percent), propylene glycol 1,2(from 10 to 90 mol percent) plus azelaic acid.

The diisocyanates which are preferred when used to form the uncureddiisocyanate-modified polyesters and polyesteramides, are 4,4 diphenyldiisocyanate; 1,5- naphthalene diisocyanate, the meta tolylenediisocyanates such as 2,4- and 2,6-to1ylene diisocyanates and4,4-cliphenylene methane diisocyanate. If meta tolylene diisocyanate isto be used, a convenient method of adding it is in the form of one ofits dimers such as the dimer of 2,4-tolylene diisocyanate of thefollowing formula:

I O I NCO g NCO The dimer is less toxic than the monomeric material.

Of the first class of elastomeric polymers described above, those ofparticular interest are the rubber-like polymers resulting frompolyethylene adipate modified by 4,4-diphenyl diisocyanate,1,5-naphthalene diisocyanate; 4,4-diphenylene methane diisocyanate, ormixtures thereof; polypropylene 1,2 adipate modified by 4,4-diphenyldiisocyanate; 1,5-naphthalene diisocyanate; 4,4- diphenylene methanediisocyanate, or mixtures thereof; polyethylene (80 mol percent)propylene 1,2 (20 mol percent) adipate modified by 4,4-diphenyldiisocyanate; 1,5-naphthalene diisocyanate; 4,4-diphenyl methanediisocyanate, or mixtures thereof; polyethylene (80 mol perment)propylene 1,2 (20 mol percent) azelate modified by 4,4-diphenyldiisocyanate; 1,5-naphthalene diisocyanate; 4,4-diphenylene methanediiso-cyanate, or mixtures thereof; and polyethylene (80 mol percent)propylene 1,2 (from 19 to 17 mol percent) piperazine (from 1 to 3 molpercent) adipate modified by 4,4-diphenyl diisocyanate; 1,5-naphthalenediisocyanate; 4,4 -diphenylene methane diisocyanate, or mixturesthereof. These polymers, when curved, have been found to possessoutstanding physical properties.

Of the second class of elastomeric polymers described above, those ofparticular interest are the rubber-like polymers resulting frompolyethylene adipate modified by a meta tolylene diisocyanate;polypropylene 1,2 adipate modified by a meta tolylene diisocyanate;polyethylene mol percent) propylene 1,2 (20 mol percent) adipatemodified by a meta tolylene diisocyanate; polyethylene (80 mol percent)propylene 1,2 (20 mol percent) azelate modified by a meta tolylenediisocyanate; and polyethylene (80 mol percent) propylene 1,2 (from 19to 17 mol percent) piperazine (from 1 to 3 mol percent) adipate modifiedby a meta tolylene diisocyanate.

Mixtures of meta tolylene diisocyanates such as mixtures of 2,4- and2,6-tolylene diisoeyanates may also be used.

Of the third class of elastomeric interpolymers described above, thoseof particular interest are the rubberlike materials resulting from:

(1) Polyethylene adipate modified by a meta tolylene diisocyanate and byethylene diamine, tetramethylene diamine, hexamethylene diamine, ethanolamine, benzidine; 4,4-diamino diphenyl methane or mixtures thereof.

(2) Polypropylene 1,2-adipate modified by 2. meta tolylene diisocyanate,and by ethylene diamine, tetramethylene diamine, hexamethylene diamine,ethanol amine, benzidine; 4,4'diamino diphenyl methane or mixturesthereof.

(3) Polyethylene (80 mol percent) propylene 1,2 (20 mol percent) adipatemodified by a meta tolylene diisocyanate, and by ethylene diamine,tetramethylene diamine, hexame'ihylene diamine, ethanol amine,benzidine; 4,4-diamino diphenyl methane or mixtures thereof.

(4) Polyethylene (80 mol percent) propylene 1,2 (20 mol percent) azelatemodified by a meta tolylene diisocyanate, and by ethylene diamine,tetramethylene diamine, hexamethylene diamine, ethanol amine, benzidine;4,4-diamino diphenyl methane or mixtures thereof.

Mixtures of meta tolylene diisocyanates such as mixtures of 2,4- and2,6-tolylene diisocyanates may also be used.

Of the fourth class of elastomeric interpolymers described above, thoseof particular interest are the rubberlike materials resulting from:

(1) Polyethylene adipate modified by 4,4-diphenyl diisocyanate; 1,5naphthalene diisocyanate; 4,4-diphenylene methane diisocyanate, ormixtures thereof, and by ethylene diamine, tetramethylene diamine,hexamethylene diamine, ethanol amine, benzidine; 4,4-diamino diphenylmethane or mixtures thereof.

(2) Polypropylene 1,2 adipate modified by 4,4-diphenyl diisocyanate;1,5-naphthalene diisocyanate; 4,4-

. diphenylene methane diisocyanate, or mixtures thereof,

and by ethylene diamine tetramethylene diamine, hexamethylene diamine,ethanol amine, benzidine; 4,4-diamino diphenyl methane or mixturesthereof.

(3) Polyethylene (80 mol percent) propylene 1,2 (20 mol percent) adipatemodified by 4,4-diphenyl diisocyanate; 1,5 naphthalene diisocyanate; 4,4diphenylene methane diisocyanate, or mixtures thereof, and by ethylenediamine, tetramethylene diamine, hexamethylene diamine, ethanol amine,benzidine; 4,4-diamino diphenyl methane or mixtures thereof.

(4) Polyethylene (80 mol percent) propylene 1,2 (20 mol percent) azelatemodified by 4,4-diphenyl diisocyanate; 1,5-naphthalene diisocyanate;4,4-diphenylene methane diisocyanate, or mixtures thereof, and 'byethylene diamine, tetramethylene diamine, hexamethylene diamine, ethanolamine, benzidine; 4,4-diamino diphenyl methane or mixtures thereof.

The following examples, in which parts are by weight, are illustrativeof the preparation of polyesters and elastomeric diisocyanate-modifiedpolyesters.

7 Example 1.Preparatin of a typical polyester Adipic acid (35l5 parts)was placed in a liter, 3- necked flask fitted with astirrer,-thermo-couple well, gas inlet tube, distilling head, .andcondenser. To the acid were added 1064 parts of ethylene glycol and 869parts of propylene 1,2 glycol. The molar ratio of dibasic acid toglycolis '1:1.19. Themixture was heated to 13 0- 160 C. until most ofthe water had distilled off. The temperature was then ,gradually'raisedto 200 C., the pressure being gradually 'reduced'to mm. and nitrogenbeing bubbled through the melt. After 23 /2 hours a soft white waxysolid was obtained. Determinations showed the acid number to be 3.5.and'the hydroxyl number to Example 2 .'Preparati0n 0f thediisocyanate-m'odified polymer A quantity of polyester was prepared fromadipic acid,

ethylene glycol and propylene 1,2 glycol according to the general methodand in substantially the same ratios as shown in Example 1. Thispolyester had an acid number of 3.1 and a hydroxyl number of 55.6. Afterheating 2270 parts of this polyester in a steamheated Baker- Perkinsmixer to 120 C., 4,4'-diphenyl diisocyanate (280.3 parts of 95.7% purityor 0.96 mols per mol of polyester) was added. After ten minutes ofmixing the hot melt was poured into a carnauba Wax coated tray and bakedfor'8 hours at 130 C. The resulting polymer had excellent processingcharacteristics on a rubber mill. Tests showed the following physicalproperties-intrinsic viscosity 1.69, percent gel 3.9, and softeningpoint 186 C.

Example' 3.-Preparati0n of the diisocyanate-modified polymer A quantityof polyester was prepared from adipic acid, ethylene glycol, andpropylene glycol 1,2 according to the general method and insubstantially the same ratios as shown in Example 1. This polyester hadan acid number of 3.1 and a hydroxyl number of 55.6. After heating 200parts of this polyster to 120 C. in an iron kettle,2,4-tolylene'diisocyanate (20.11 parts of 99.7 purity or 1.10 mols permol of polyester) was added. After 15 minutes of mixing, the materialwas poured into a waxed aluminum tray and baked for 8 hours at 120 C.The resultingpolymer had excellent processing characteristics on arubber mill.

A convenient method of determining the effect of using theamine/aldehydecondensation product in accelerating the reaction betweenthe polyisocyanate and the clastomeric diisocyanate-modified, polyesteris to run a plastic flow test upon the elastomeric compositions. Thistest comprises extruding the compounded material through an orificeunder a constant pressure (.1500 pounds per square inch) and at aconstant temperature (212 F.) and recording the time (in seconds)required to extrude a given length through said orifice. 'The timenecessary to extrude a given length through the orifice will, of course,increase as the compounded material becomes less plastic and begins tocure or cross-link.

Listed below are plastic flow data showing the'results obtained usingvarious tertiary amines as accelerators or catalyst-s. Recipes are shownin parts by weight.

The elastomer shown was prepared'aceording to Example 2. The elastomer,diisocyanate, and accelerator were mixed togther on a rubber mill. Thesamples were aged at room temperature for the indicated time before theplastic flow tests were run. The plastieflow data are expressedinseconds per inch, the tests being run at a pressure of 1500 pounds persquare inch and atemperatureof 212F. l

Analysis of Table I will indicate that the condensation productsfunction as accelerators for therreaction between the polyisocyanateandthe diisocyanate-modified polyester, since the plastic flow results,expressed in seconds per inch, show that the f'accelerated compoundsdisplayincreased resistance to flow which indicates that they toughen orcure at a muchfaster rate than do theun-accelerated compounds.

This application is a 'continuation-in-part ofour. copend'mg applicationSerial Number 322,564, filed N0- vern'ber 25, 1952, .now abandoned.

While certain representative embodiments and details have been shownforthe purpose of illustrating the invention, it will be apparent to thoseskilled in this art that various changes anud, modifications may be madetherein without departing fromthe spirit or scope of the inven' tion.

We claim: 7

l. The method of catalyzing the reaction between an uncured elastomericdiisocyanate-modified polymer and a polyisocyanate which comprisesconducting said reaction in thepresence of a condensation productresulting from the reaction between approximately one mol of an organicprimary amine and selected from the, group con-v sisting of aniline,butylamine,,methy1amine, o-toluidine' and diethylamine and from twoto'five mols of an aliphatic aldehyde having a plurality of carbon atomsand selected from the group consisting of propionaldehyde,butyraldehyde, heptaldehyde, and benzaldehyde, said elastomericdiisocyanate-modified polymer being selected from the group consistingof (A) the reaction product resulting from the reaction of a mixturecomprising: (1)

a material prepared from 'bifunctional' ingredients includ-' ing atleast one di-carboxylic acid and at least one complementary bifunctionalreactant in which the functional groups are selected from the classconsisting of the hydroxyl group and the hydrogen-bearing amino groups,the hydrogen-bearing amino groups being present in an amount nottoexceed 7.5% of the total bifunctional reactant, said material having ahydroxyl number from 40 to and an acid number from 0 to 7, and (2) atleast one diisocyanate selectedfrom the-group consisting of 4,4-diphenyldiisocyanate; 4,4'- diphenylene-methane diisocyanate, dianisidinediisocyanate; 4,4'-tolidine diisocyanate; 1,5-naphthalene diisocyanate;4,4'-diphenyl etherdiisocyanate, and p-phenylene diisocyanate, thediisocyanate being used in an amount ranging from 0.70 to 0.99 mol permol of said material; (B) the reaction product resulting from thereaction of a mixture comprising: (1) a material prepared frombifunctional ingredients including at least one dicarboxylic acid and atleast one complementary bifunctional reactant in which the functionalgroups are selected from the class consisting of the hydroxyl group andthe hydrogen-bearing amino groups, the hydrogen-bearing amino groupsbeing present in an amount not to exceed 30% of the total functionalgroups of said complementary bifunctional reactant, said material havinga hydroxyl number from 30 to and an acid number from 0 to 12, and (2) atleast one tolylene diisocyanate used in an amount ranging from 0.85 to1.10, mols per mol of said material; (C) the reaction product resultingfrom the reaction of a mixture comprising: (1) a polyester prepared frombifunctional ingredients including at least one dicarboxylic acidcontaining at least three carbon atoms and at least one glycol, saidpolyester having a hydroxyl number from 30 to 140 and anacid number from0 to 12, (2) at least one bifunctional addi tive selected from the groupconsisting of diamines, amino alcohols, dicarboxylic acids, aminocarboxylic acids, hydroxy carboxylic acids and the ureas, guanidines,and thioureas containing a primary amino group, said bifunctionaladditive being used in an amount such that the total number of -NH andCOOH equivalents present in said bifunctional reactant shall be from0.06 to 0.24 equivalents per mol of polyester, and (3) at least onetolylene diisocyanate used in an amount equal to the sum of from 0.85mols to 1.10 mols of diisocyanate per mol of polyester plus the molaramount of diisocyanate equivalent to the mols of said bifunctionaladditive used; (D) the reaction product resulting from the reaction of amixture comprising: (1) a polyester prepared from bifunctionalingredients including at least one dicarboxylic acid containing at leastthree carbon atoms and at least one glycol, said polyester having ahydroxyl number from 40 to 100 and an acid number from O to 7, (2) atleast one bifunctional additive selected from the group consisting ofdiamines, amino alcohols, dicarboxylic acids, amino carboxylic acids,hydroxy carboxylic acids and the ureas, guanidines, and thioureascontaining a primary amino group, said bifunctional additive being usedin an amount such that the total number of NH and COOH equivalentspresent in said bifunctional reactant shall be from 0.06 to 0.48equivalents per mol of polyester, and (3) at least one diisocyanateselected from the group consisting of 4,4'-diphenyl diisocyanate;4,4-diphenylene methane diisocyanate; 4,4-tolidine diisocyanate,dianisidine diisocyanate; 1,5-naphthalene diisocyanate; 4,4'-diphenylether diisocyanate, and p-phenylene diisocyanate, the diisocyanate beingused in an amount equal to the sum of from 0.70 mols to 0.99 mols ofdiisocyanate per mol of polyester plus the molar amount of diisocyanateequivalent to the mols of bifunctional addifive used.

2. The method defined by claim 1 in which the condensation product isformed from approximately four mols of butyraldehyde and approximatelyone mol of aniline.

3. The method defined by claim 1 in which the condensation product isformed from approximately four mols of butyraldehyde and one mol ofbutylamine.

4. The method defined by claim 1 in which the elastomericdiisocyanate-modified polymer is one resulting fiom the reaction of amixture comprising (A) a polyester prepared from at least onedicarboxylic acid and at least one glycol, said polyester having ahydroxyl number from 30 to and an acid number from 0 to 12 and (B)tolylene diisocyanate used in an amount ranging from 0.90 to 1.00 molper mol of said polyester.

5. The method defined by claim 1 in which the elastomericdiisocyanate-modified polymer is one resulting from the reaction of amixture comprising: (A) a polyester prepared from at least onedicarboxylic acid containing at least three carbon atoms and at leastone glycol, said polyester having a hydroxyl number from 30 to 140 andan acid number from 0 to 12 (B) a diamine used in an amount such thatthe total number of NH equivalents is from 0.06 to 0.24 equivalent permol of polyester and (C) tolylene diisocyanate used in an amount equalto the sum of from 0.90 to 1.00 mol per mol of polyester plus the molaramount of diisocyanate equivalent to the mols of diamine used.

References Cited in the file of this patent UNITED STATES PATENTSWilliams et a1. Nov. 4, 1930 Burnett Nov. 4, 1930 UNITED STATES PATENT@FFTQE QERTTTTQATE QT RECTTN Nelson Va Seeger et al Signed and sealedthis 11th day of November 1958,

(SEAL) Attest: KARL Ho AXLINE RUBERT 3. WATSON Attesting OficerCommissioner of Patents

1. THE METHOD OF CATALYZING THE REACTION BETWEEN AN UNCURED ELASTOMERICDIISOCYANATE-MODIFIED POLYMER AND A POLYISOCYANATE WHICH COMPRISESCONDUCTING SAID REACTION IN THE PRESENCE OF A CONDENSATION PRODUCTREACTION IN THE PRESENCE OF A CONDENSATION PRODUCT RESULTING ORGANICPRIMARY AMINE AND SELECTED FROM THE GROUP CONSISTING OF ANILINE,BUTYLAMINE, METHYLAMINE, O-TOLUIDINE AND DIETHYLAMINE AND FROM TOW TOFIVE MOLS OF AN ALIPHATIC ALDEHYDE HAVING A PLURALITY OF CARBON ATOMSAND SELECTED FROM THE GROUP CONSISTING OF PROPIONALDEHYDE,BUTYRALDEHYDE, HEPTALDEHYDE, AND BENZALDEHYDE, SAID ELASTOMERICDIISOCYANATE-MODIFIED POLYMER BEING SELECTED FROM THE GROUP CONSISTINGOF (A) THE REACTION PRODUCT RESULTING FROM THE REACTION OF A MIXTURECOMPRISING: (1) A MATERIAL PREPARED FROM BIFUNCTIONAL INGREDIENTSINCLUDING AT LEAST ONE DI-CARBOXULIC ACID AND AT LEAST ONE COMPLEMENTARYBIFUNCTIONAL REACTANT IN WHICH THE FUNCTIONAL GROUPS ARE SELECTED FROMTHE CLASS CONSISTING OF THE HYDROXYL GROUP AND THE HYDROGEN-BEARINGAMINO GROUPS, THE HYDROGEN-BEARING AMINO GROUPS BEING PRESENT IN ANAMOUNT NOT TO EXCEED 7.5% OF THE TOTAL BIFUNCTIONAL REACTANT, SAIDMATERIAL HAVING A HYDRODYL NUMBER FROM 40 TO 100 AND AN ACID NUMBER FROM0 TO 7, AND (2) AT LEAST ONE DIISOCYANATE SELECTED FROM THE GROUPCONSISTING OF 4,4''-DIPHENYL DIISOCYANATE; 4,4''- DIPHENYLENE METHANEDIISOCYANATE, DIANISIDINE DIISOCYANATE; 4,4''-TOLIDINE DIISOCYANATE;1,5-NAPHTHALENE DIISOCYANATE; 4,4''-DIPHENYL ETHER DIISOCYANATE, ANDP-PHENYLENE DIISOCYANATE, THE DIISOCYANATE BEING USED IN AN AMOUNTRANGING FROM 0.70 TO 0.99 MOL PER MOL OF SAID MATERIAL; (B) THE REACTIONPRODUCT RESULTING FROM THE REACTION OF A MIXTURE COMPRISING: (1) AMATERIAL PREPARED FROM BIFUNCTIONAL INGRDIENTS INCLUDING AT LEAST ONEDICARBOXYLIC ACID AND AT LEAST ONE COMPLEMENTARY FIBUNCTIONAL REACTANTIN WHICH THE FUNCTIONAL GROUPS ARE SELECTED FROM THE CLASS CONSISTING OFTHE HYDROXYL GROUP AND THE HYDROGEN-BEARING AMINO GROUPS, THEHYDROGEN-BEARING AMINO GROUPS BEING PRESENT IN AN AMOUNT NOT TO EXCEED30% OF THE TOTAL FUNCTIONAL GROUPS OF SAID COMPLEMENTARY BIFUNCTIONALREACTANT, SAID MATERIAL HAVING A HYDROXYL NUMBER FROM 30 TO 140 AND ANACID NUMBER FROM 0 TO 12, AND (2) AT LEAST ONE TOLYLENE DIISOCYANATEUSED IN AN AMOUNT RANGING FROM 0.85 TO 1.10 MOLS PER MOL OF SAIDMATERIAL; (C) THE REACTION PRODUCT RESULTING FROM THE REACTION OF AMIXTURE COMPRISING: (1) A POLYESTER PREPARED FROM BIFUNCTIONALINGREDIENTS INCLUDING AT LEAST ONE DICARBOXYLIC ACID CONTAINING AT LEASTTHREE CARBON ATOMS AND AT LEAST ONE GLYCOL, SAID POLYESTER HAVING AHYDROXYL NUMBER FROM 30 TO 140 AND AN ACID NUMBER FROM 0 TO 12, (2) ATLEAST ONE BIFUNCTIONAL ADDITIVE SELECTED FROM THE GROUP CONSISTING OFDIAMINES, AMINO ALCOHOLS, DICARBOXYLIC ACIDS, AMINO CARBOXYLIC ACIDS,HYDROXY CARBOXULIC ACIDS AND THE UREAS, GUANIDINES, AND THIOUREASCONTAINING A PRIMARY AMINO GROUP, SAID BIFUNCTIONAL ADDITIVE BEING USEDIN AN AMOUNT SUCH THAT THE TOTAL NUMBER OF -NH2 AND -COOH EQUIVALENTSPRESENT IN SAID BIFUNCTIONAL REACTANT SHALL BE FROM 0.0L TO 0.24EQUIVALENTS PER MOL OF POLYESTER, AND (3) AT LEAST ONE TOLYLENEDIISOCYANATE USED IN AN AMOUNT EQUAL TO THE SUM OF FROM 0.85 MOLS TO1.10 MOLS OF DIISOCYANATE PER MOL OF POLYESTER PLUS THE MOLAR AMOUNT OFDIISOCYANATE EQUIVALENT TO THE MOLS OF SAID BIFUNCTIONAL ADDITIVE USED;(D) THE REACTION PRODUCT RESULTING FROM THE REACTION OF A MIXTURECOMPRISING: (1) A POLYESTER PREPARED FROM BIFUNCTIONAL INGREDIENTSINCLUDING AT LEAST ONE DICARBOXYLIC ACID CONTAINING AT LEAST THREECARBON ATOMS AND AT LEAST ONE GLYCOL, SAID POLYESTER HAVING A HYDROXYLNUMBER FROM 40 TO 100 AND AN ACID NUMBER FROM 0 TO 7, (2) AT LEAST ONEBIFUNCTIONAL ADDITIVE SELECTED FROM THE GROUP CONSISTING OF DIAMINES,AMINO ALCOHOLS, DICARBOXYLIC ACIDS, AMINO CARBOXYLIC ACIDS, HYDROXYCARBOXYLIC ACIDS AND ESTER, AND (3) AT LEAST ONE DIISOCYANATE SELECTEDFROM THE GROUP CONSISTING OF 4,4''-DIPHENYL DIISOCYANATE;4,4''-DIPHENYLENE METHANE DIISOCYANATE; 4,4''-TOLIDINE DIISOCYANATE;4,4''-DIPHENYL ETHER DIISOCYANATE, AND P-PHENYLENE NATE; 4,4''-DIPHENYLETHER DIISOCYANATE, AND P-PHENYLENE DIISOCYANATE, THE DIISOCYANATE BEINGUSED IN AN AMOUNT EQUAL TO THE SUM OF FROM 0.70 MOLS TO 0.99 MOLS OFDIISOCYANATE PER MOL OF POLYESTER PLUS THE MOLAR AMOUNT OF DIISOCYANTEEQUIVALENT TO THE MOLS OF BIFUNCTIONAL ADDITIVE USED.